Synthesis and gas permeability of novel fluorinated poly(phenylene-co-naphthalimide)s

A new class of high-performance polymers [poly(phenylene-co-naphthalimide)s] was prepared through the Ni(0) catalytic coupling of N-(4-chloro-2-trifluromethylphenyl)-5-chloro-1,8-naphthalimide and 2,5-dichlorobenzophenone. The resulting copolymers exhibited high molecular weights (high inherent viscosities) and a combination of desirable properties such as good solubility in dipolar aprotic solvents, film-forming capability, and mechanical properties. The glass-transition temperatures of the copolymers ranged from 320 to 403 degrees C and increased as the content of the naphthalimide moiety increased. Tough polymer films, obtained via casting from N-methylpyrrolidone solutions, had tensile strengths of 64-107 MPa and tensile moduli of 3.4-4.7 GPa. The gas permeability coefficients of the copolymers were measured for H-2, CO2, O-2, CH4, and N-2. They showed oxygen permeability coefficients and permeability selectivity of oxygen to nitrogen (permeability coefficient for O-2/permeability coefficient for N-2) in the ranges of 1.39-4.31 and 4.92-5.38 barrer, respectively.

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .2.

Gas permeability coefficients of a series of aromatic polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) with various aromatic diamines, to H-2, O-2 and N-2 have been measured under 7 atm and at the temperature range 30-100 degrees C. A significant change in the permeability and permselectivity resulting from the systematic variation in chemical structure of the polyetherimides was found. Among the polyetherimides, that were prepared from phenylenediamine and methyl substituted phenylenediamines, the increase of permeability is accompanied by a decrease of permselectivity. The polyetherimides that were prepared from 3,5-diaminobenzoic esters have lower permselectivity than the others. However, the polyetherimide from 3,5-diaminobenzoic acid possesses much higher permselectivity than the others due to cross-linking. Copyright (C) 1996 Elsevier Science Ltd

Effects of molecular structure on the permeability and permselectivity of aromatic polyimides

Permeability coefficients of H-2, O-2, and N2 were measured under 10 atm at the temperature from ambient temperature up to 150 degrees C in a series of structurally different aromatic homo- and copolyimides, which were prepared from 4,4'-oxydianiline (ODA) or 4,4'-methylene dianiline (MDA) with various aromatic dianhydrides. The study shows that the molecular structure of the polyimides strongly influences gas permeability and permselectivity. As a result, the permeability coefficients of the polyimide membranes for each gas vary by over two orders of magnitude. In general, among the polyimide membranes studied, the increase in permeability of polymers is accompanied by the decrease in permselectivity, and the MDA-based polyimide membranes have higher permeability than ODA-based ones. Among the polyimides prepared from bridged dianhydrides, the permeability coefficients to H-2, O-2, and N-2 are progressively increased in the order BPDA < BTDA < ODPA similar to TDPA < DSDA ( SiDA < 6FDA, while H-2/N-2 and O-2/N-2 permselectivity coefficients are progressively decreased in the same order. The copolyimide membranes, which were prepared from 3,3',4,4' biphenyltetracarboxylic dianhydride (BPDA), bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride (SiDA), and ODA, have favorable gas separation properties and are useful for H-2/N-2 separation applications. (C) 1996 John Wiley & Sons, Inc.

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .1.

Gas permeability coefficients of a series of aromatic polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) and various aromatic diamines, to H-2, CO2, O-2, N-2 and CH4 have been measured under 7 atm pressure and over the temperature range 30-150 degrees C. A significant change in permeability and permselectivity, which resulted from a systematic variation in chemical structure of the polyetherimides, was found. Generally, increases in permeability of the polyetherimides are accompanied by decreases in permselectivity. The order of decrease of the permeability coefficients is as follows: HQDPA-IPDA > HQDPA-DDS > HQDPA-MDA > HQDPA-ODA > HQDPA-DABP > HQDPA-BZD. However, HQDPA-DMoBZD and HQDPA-DMoMDA, with bulky methoxy side-groups on the aromatic rings of the diamine residue, display both high permeability coefficients and high permselectivity. The favourable gas separation property, excellent thermal and chemical stability, and high mechanical strength make HQDPA-DMoBZD and HQDPA-DMoMDA promising candidates for membrane-based gas separation applications.

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .3.

Gas permeability coefficients of a series of aromatic polyetherimides prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) and four (methylene dianiline)s with a methyl side group to H-2, CO2, O-2, N-2, and CH4 were measured under 7 atm and within a temperature range from 30 to 150 degrees C. The gas permeabilities and permselectivities of these polymers were compared with those of the HQDPA-based polyetherimides from methylene dianiline (MDA) and isopropylidene dianiline (IPDA). The number and position of the methyl side groups on the benzene rings of the diamine residues strongly affect the gas permeabilities and permselectivities of the HQDPA-based polyetherimides. The gas permeability of the polyetherimide progressively increases with an increase in the number of the methyl side groups. Both the gas permeability and permselectivity of the polyetherimides with methyl side groups are higher than those of HQDPA-MDA. The polyetherimide prepared from 3,3'-dimethyl 4,4'-methylene dianiline (DMMDA1) possesses both higher permeability and permselectivity than the polyetherimides prepared from 2,2'-dimethyl 4,4'-methylene dianiline (DMMDA2). However, two of the polyetherimides prepared 2,2',3,3'-tetramethyl 4,4'-methylene dianiline (TMMDA1) or 2,2', 5,5'-tetramethyl 4,4'-methylene dianiline (TMMDA2) possess almost the same gas permeability and permselectivity.

The Interaction Between Shock Waves and Foam in a Shock Tube

An experimental study and a numerical simulation were conducted to investigate the mechanical and thermodynamic processes involved in the interaction between shock waves and low density foam. The experiment was done in a stainless shock tube (80mm in inner diameter, 10mm in wall thickness and 5360mm in length). The velocities of the incident and reflected compression waves in the foam were measured by using piezo-ceramic pressure sensors. The end-wall peak pressure behind the reflected wave in the foam was measured by using a crystal piezoelectric sensor. It is suggested that the high end-wall pressure may be caused by a rapid contact between the foam and the end-wall surface. Both open-cell and closed-cell foams with different length and density were tested. Through comparing the numerical and experimental end-wall pressure, the permeability coefficients a and 0 are quantitatively determined.

Synthesis and properties of novel regioirregular polyimides from easily synthesized asymmetrical dichlorophthalimide monomers

New asymmetrical aromatic dichlorophthalimide monomers containing pendant groups (trifluoromethyl or methyl) were conveniently prepared from inexpensive and commercially available compounds. With these monomers, a new class of soluble polyimides with a regioirregular structure within the polymer backbone was obtained by the Ni(0)-catalyzed polymerization method. The structures of the polymers were confirmed by various spectroscopic techniques. The polyimides displayed better solubility and higher thermal stability than the corresponding regular polyimides. In addition, fluorinated polyimides in this study had low dielectric constants ranging from 2.52 to 2.78, low moisture absorptions of less than 0.59%, and low thermal expansion coefficients between 10.6 and 19.7 ppm/degrees C. The oxygen permeability coefficients and permeability selectivity of oxygen to nitrogen of the films were in the ranges of 2.99-4.20 barrer and 5.55-7.50, respectively. We have demonstrated that the synthetic pathway for polyimides provides a successful approach to increasing the solubility and processability of polyimides without sacrificing their thermal stability.

Synthesis and gas transport property of polyimide from 2,2 '-disubstituted biphenyltetracarboxylic dianhydrides (BPDA)

A series of dianhydride monomers, 2,2'-disubstituted-4,4',5,5'-biphenyltetracarboxylic dianhydride (substituents = phenoxy, p-methylphenoxy, p-tert-butylphenoxy, nitro, and methoxy) were synthesized by the nitration of an N-methyl protected 3,3',4,4'-biphenyttetracarboxylic dianhydride (BPDA) and subsequent aromatic nucleophilic substitutions with aroxides (NaOAr) or methoxide. These dianhydrides were polymerized with various aromatic diamines in refluxing m-cresol containing isoquinoline to afford a series of aromatic polyintides. The effects of varying 2,2'-substituents of the dianhydride (BPDA) moiety on the properties of polyimides were investigated. It was found that polyimides from the dianhydrides containing phenoxy, p-methylphenoxy, and p-tert-butylphenoxy side groups possessed excellent solubility and film forming capability whereas polyimides from 2,2'-dinitro-BPDA and 2,2'-dimethoxy-BPDA were less soluble in organic solvent. The soluble polymers formed flexible, tough and transparent films. The films had a tensile strength, elongation at break, and Young's modulus in the ranges 102-168 MPa, 8-21%, 2.02-2.38 GPa, respectively. The polymer gas permeability coefficients (P) and ideal selectivities for N-2, O-2, CO2 and CH4 were determined for the -OAr substituted polyimides. The oxygen permeability coefficient (P-O2) and permselectivity of oxygen to nitrogen (PO2/N-2) of the films were in the ranges 3.4-11.3 barrer and 3.8-4.6, respectively.

Synthesis and properties of novel fluorinated poly(phenylene-co-imide)s

A new class of high-performance materials, fluorinated poly(phenylene-co-imide)s, were prepared by Ni(0)-catalytic coupling of 2,5-dichlorobenzophenone with fluorinated dichlorophthalimide. The synthesized copolymers have high molecular weights ((M) over bar (W)= 5.74 x 10(4)-17.3 x 10(4) g center dot mol(-1)), and a combination of desirable properties such as high solubility in common organic solvent, film-forming ability, and excellent mechanical properties. The glass transition temperature (T(g)s) of the copolymers was readily tuned to be between 219 and 354 degrees C via systematic variation of the ratio of the two comonomers. The tough polymer films, obtained by casting from solution, had tensile strength, elongation at break, and tensile modulus values in the range of 66.7-266 MPa, 2.7-13.5%, and 3.13-4.09 GPa, respectively. The oxygen permeability coefficients (P-O2) and permeability selectivity of oxygen to nitrogen (P-O2/P-N2) of these copolymer membranes were in the range of 0.78-3.01 barrer [1 barrer = 10(-10) cm(3) (STP) cm/(cm(2) center dot s center dot cmHg)] and 5.09-6.2 5, respectively. Consequently, these materials have shown promise as engineering plastics and gas-separation membrane materials.

Synthesis, properties, and gas permeation performance of cardo poly(arylene ether sulfone)s containing phthalimide side groups

Novel bisphenol monomers (1a-d) containing phthalimide groups were synthesized by the reaction of phenolphthalein with ammonia, methylamine, aniline, and 4-tert-butylanilne, respectively. A series of cardo poly (arylene ether sulfone)s was synthesized via aromatic nucleophilic substitution of 1a-d with dichlorodiphenylsulfone, and characterized in terms of thermal, mechanical and gas transport properties to H-2, O-2, N-2, and CO2. The polymers showed high glass transition temperature in the range 230-296 degrees C, good solubility in polar solvents as well as excellent thermal stability with 5% weight loss above 410 degrees C. The most permeable membrane studied showed permeability coefficients of 1.78 barrers to O-2 and 13.80 barrers to CO2, with ideal selectivity. factors of 4.24 for O-2/N-2 pair and 28.75 for CO2/CH4 pair. Furthermore, the structure-property relationship among these cardo poly(arylene ether sulfone)s had been discussed on solubility, thermal stability, mechanical, and gas permeation properties. The results indicated that introducing 4-tert-butylphenyl group improved the gas permeability of polymers evidently.

Synthesis and characterization of soluble poly(amideimide)s bearing triethylamine sulfonate groups as gas dehumidification membrane material

A series of soluble poly(amide-imide)s (PAIs) bearing triethylammonium sulfonate groups were synthesized directly using trimellitic anhydride chloride (TMAC) polycondensation with sulfonated diamine such as 2,2'-benzidinedisulfonic acid (BDSA), 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS), and nonsulfonated diamine 4,4-diaminodiphenyl methane in the presence of triethylamine. The resulting copolymers exhibited high molecular weights (high inherent viscosity), and a combination of desirable properties such as good solubility in dipolar aprotic solvents, film-forming capability, and good mechanical properties. Wide-angle X-ray diffraction revealed that the polymers were amorphous. These copolymers showed high permeability coefficients of water vapor because of the presence of the hydrophilic triethylammonium sulfonate groups. The water vapor permeability coefficients (P-w) and permselectivity coefficients of water vapor to nitrogen and methane [alpha(H2O/N-2) and (alpha(H2O/CH4)] Of the films increased with increasing the amount of the triethylammonium sulfonated groups.

Barrier properties of vinylidene chloride methyl acrylate copolymer

A series of vinylidene dichloride (VDC) copolymers with methyl acrylate (MA) as comonomer (3-12wt%), was prepared by free-radical suspension copolymerization. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor were measured at 30 degrees C and 100% relative humidity. All the VDC/MA copolymers studied are semicrystalline. As the MA content increases, the permeability coefficients of the copolymers to oxygen, carbon dioxide, and water vapor are progressively increased, caused by decrease in crystalline fraction and increase in free volume of VDC/MA copolymers.

Relationship between structure and gas permeation properties of polyimides prepared from oxydiphthalic dianhydride

Gas permeability coefficients of a series of aromatic polyimides, which were prepared from oxydiphthalic dianhydride (ODPA) with various aromatic diamines, with respect to H-2, CO2, O-2, N-2, and CH4 were measured under 10 atm and in the temperature range from 30 to 150 degrees C. A significant change in gas permeability and permselectivity resulting from systematic variation of the chemical structure of the polyimides was found. Among the polyimides which were prepared from phenylenediamine and its derivatives as well as bridged diamines without side groups on the benzene rings of the diamine residues, the increase of the gas permeability is accompanied by a decrease of the permselectivity. However, both the gas permeability and the permselectivity of the polyimides which were prepared from bridged diamines with methyl or methoxy groups on the benzene rings of the diamine residues simultaneously increase.

Barrier property and structure of acrylonitrile/acrylic copolymers

A series of acrylonitrile (AN) copolymers with methyl acrylate (MA) or ethyl acrylate (EA) as comonomer (5-23 wt%) was prepared by free-radical copolymerisation. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor also measured at 100% relative humidity and at 30 degrees C. All the AN/acrylic copolymers are semicrystalline. As the acrylate content increase, the permeability coefficients of the copolymers to oxygen and carbon dioxide are increased progressively, but those to water vapor are decreased progressively. The gas permeability coefficients of the polymers were correlated with free-volume fractions or the ratio of free volume to cohesive energy.

Novel poly(aryl ether ketone)s containing various pendant groups .2. Gas-transport properties

The gas transport of hydrogen, oxygen, nitrogen, carbon dioxide, and methane gases in a series of poly(aryl ether ketone)s was examined. These polymer membranes have a wide range of permeability coefficients and permselectivity coefficients, showing excellent gas-transport properties. The enhanced interchain interaction in the polymers due to intermolecular hydrogen bonds and ionic bonds results in a considerable increase in permselectivity but a decrease in permeability. On the contrary, the polymers with bulky arkyl substituents show significantly increased permeability. The causes of this trend are interpreted in terms of the free volume, interchain distance, and glass transition temperature together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest is the observation that the ionomer IMPEK-K+, which simultaneously contains bulky isopropyl substituents and pendant carboxylate groups, exhibits over twice higher CO2 permeability and 15% higher CO2/CH4 permselectivity than those of bisphenol-A p'olysulfone (PSF). The possibility of using the new synthesized poly(aryl ether ketone)s in gas separation membrane application is also discussed. (C) 1997 John Wiley & Sons, Inc.